Optical compensatory sheet comprising transparent support and optically anisotropic layer

ABSTRACT

An optical compensatory sheet comprises a transparent support and an optically anisotropic layer. The optically anisotropic layer is formed from liquid crystal molecules and monomers having four or more double bonds. The monomers are polymerized to form a polymer in the optically anisotropic layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of Application No. 10/052,440, filedJan. 23, 2002, the contents of which are incorporated herein byreference.

FIELD OF THE INVENTION

The present invention relates to an optical compensatory sheetcomprising a transparent support and an optically anisotropic layerformed from liquid crystal molecules. The invention also relates to aliquid crystal display having the optical compensatory sheet.

BACKGROUND OF THE INVENTION

A liquid crystal display comprises a liquid crystal cell and apolarizing plate. In a liquid crystal display of transmission type, twopolarizing plates are placed on both sides of the liquid crystal cell.On the other hand, a liquid crystal display of reflection type comprisesa reflection plate, a liquid crystal cell and one polarizing plate inthis order.

The liquid crystal cell comprises a pair of substrates, rod-like liquidcrystal molecules and an electrode layer. The rod-like liquid crystalmolecules are provided between the substrates. The electrode layer has afunction of applying a voltage to the rod-like liquid crystal molecules.Various display modes are proposed according to alignment of therod-like liquid crystal molecules in the cell. Examples of the displaymodes for transmission type include TN (twisted nematic) mode, IPS(in-plane switching) mode, FLC (ferroelectric liquid crystal) mode, OCB(optically compensatory bend) mode, STN (super twisted nematic) mode,ECB (electrically controlled birefringence) mode and VA (verticallyaligned) mode. Examples of the modes for reflection type include TN modeand HAN (hybrid aligned nematic) mode.

A liquid crystal display usually comprises an optical compensatory sheet(phase retarder) as well as the liquid crystal cell and the polarizingplate. The optical compensatory sheet prevents the displayed image fromundesirable coloring. The optical compensatory sheet has anotherfunction of enlarging a viewing angle of a liquid crystal cell. In adisplay of transmission type, one or two optical compensatory sheets areplaced between the liquid crystal cell and the polarizing plate. In adisplay of reflection type, one optical compensatory sheet is placedbetween the liquid crystal cell and the polarizing plate.

A stretched birefringent polymer film has been conventionally used asthe optical compensatory sheet.

An optical compensatory sheet comprising a transparent support and anoptically anisotropic layer formed from liquid crystal molecules(particularly, discotic liquid crystal molecules) has recently beenproposed in place of the stretched birefringent polymer film. Theoptically anisotropic layer is formed by aligning the liquid crystalmolecules and fixing alignment of the molecules. The liquid crystalmolecules inherently have large birefringence and various alignmentforms. Therefore, an optical compensatory sheet obtained from the liquidcrystal molecules has a specific optical characteristic that cannot beobtained from the conventional stretched birefringent polymer film.

The optical characteristic of the optical compensatory sheet is designedaccording to that of the liquid crystal cell, namely, according todisplay mode of the liquid crystal cell. If the optical compensatorysheet is made with liquid crystal molecules (particularly, discoticliquid crystal molecules), various optical characteristics can bedesigned according to the display mode of the liquid crystal cell.

Various optical compensatory sheets using discotic liquid crystalmolecules have been proposed for liquid crystal cells of various displaymodes. For example, an optical compensatory sheet for liquid crystalcell of TN mode is described in Japanese Patent Provisional PublicationNo. 6(1994)-214116, U.S. Pat. Nos. 5,583,679, 5,646,703 and GermanPatent Publication No. 3,911,620A1. An optical compensatory sheet forliquid crystal cell of IPS or FLC mode is described in Japanese PatentProvisional Publication No. 10(1998)-54982. An optical compensatorysheet for OCB or HAN mode is described in U.S. Pat. No. 5,805,253 andInternational Patent Application No. WO96/37804. An optical compensatorysheet for STN mode is described in Japanese Patent ProvisionalPublication No. 9(1997)-26572. An optical compensatory sheet for VA modeis described in Japanese Patent No. 2,866,372.

In preparation of a liquid crystal display, the parts of the displaysuch as the liquid crystal cell, the polarizing plate and the opticalcompensatory sheet are laminated in order with an adhesive. The opticaldirections (e.g., polarizing axis, slow axis) of the cell, thepolarizing plate and the compensatory sheet must be strictly adjustedaccording to the displaying mode of the cell. It is, however, impossibleto avoid producing some failed displays in which the optical directionsof the laminated parts are improperly arranged. The parts in suchdisplay are preferably delaminated to reuse them.

The optical compensatory sheet is often destroyed while the sheet ispeeled from the liquid crystal cell. The destroyed sheet cannot bereused. Further, the fragments of the sheet remaining on the liquidcrystal cell must be removed to reuse the cell.

Accordingly, it has been wanted to improve the mechanical strength ofthe optical compensatory sheet without affecting its optical characters.

Japanese Patent Provisional Publication No. 8(1996)-27284 discloses astrong optical compensatory sheet. In preparation of the sheet, discoticliquid crystal molecules having polymerizable groups are aligned, andpolymerized to improve the mechanical strength of the sheet.

Japanese Patent Provisional Publication No. 9(1997)-152509 disclosesanother strong optical compensatory sheet. In preparation of the sheet,polymerizable groups are introduced into not only discotic liquidcrystal molecules but also a polymer of an orientation layer providedbetween a transparent support and an optically anisotropic layer.Accordingly, the polymer and the discotic liquid crystal molecules areco-polymerized along an interface between the orientation layer and theoptically anisotropic layer.

Japanese Patent Provisional Publication No. 2000-235117 discloses anoptical compensatory sheet in which a transparent support and anoptically anisotropic layer are combined with a peel strength of 400g/cm or more. Inorganic fine particles are added into the transparentsupport, the orientation layer or the optically anisotropic layer toimprove the peel strength.

SUMMERY OF THE INVENTION

A mechanically strong optical compensatory sheet can be preparedaccording to the descriptions of Japanese Patent Provisional PublicationNos. 8(1996)-27284, 9(1997)-152509 and 2000-235117.

However, the applicant has found that the improved optical compensatorysheet still sometimes breaks, and partially remains on the substrate ofthe cell when the sheet is peeled from the liquid crystal cell. Thetrouble occurs once per 10 to 100 times. Accordingly, the mechanicalstrength of the compensatory sheet should be further improved to reusethe optical compensatory sheet peeled from the liquid crystal cell.

An object of the present invention is to provide an optical compensatorysheet further improved in mechanical strength.

Another object of the invention is to provide an optical compensatorysheet can be reused even if the sheet is improperly laminated inpreparation of a liquid crystal display.

The present invention provides an optical compensatory sheet comprisinga transparent support and an optically anisotropic layer, wherein theoptically anisotropic layer is formed from liquid crystal molecules andmonomers having four or more double bonds, said monomers beingpolymerized to form a cross-linked polymer in the optically anisotropiclayer.

The invention also provides a liquid crystal display comprising twopolarizing plates, a liquid crystal cell provided between the plates,and at least one optical compensatory sheet placed between the cell andat least one of the plates, said optical compensatory sheet comprising atransparent support and an optically anisotropic layer, wherein theoptically anisotropic layer formed from liquid crystal molecules andmonomers having four or more double bonds, said monomers beingpolymerized to form a polymer in the optically anisotropic layer.

The applicant has noted that the number of double bonds (which functionas polymerizable groups) should be increased in the opticallyanisotropic layer to improve the mechanical strength of the compensatorysheet.

The method disclosed in Japanese Patent Provisional Publication No.8(1996)-27284, in which polymerizable groups are introduced into liquidcrystal molecules in the optically anisotropic layer, is very effectivein improving the mechanical strength. However, only a limited number ofthe polymerizable groups can be introduced because the structure and theamount of the liquid crystal molecules must be determined inconsideration of optical characters, which is the most important factorof liquid crystal. Therefore, the amount of the polymerizable groupscannot be determined only in consideration of the mechanical strength.

The method disclosed in Japanese Patent Provisional Publication No.9(1997)-152509, in which polymerizable groups are introduced into apolymer of an orientation layer, is effective in reinforcing only theinterface between the orientation layer and the optically anisotropiclayer. Accordingly, the polymerizable groups of the polymer cannotimprove the mechanical strength of the optically anisotropic layeritself. In the case where the optically anisotropic layer is relativelythick (for example, the thickness is 1.5 μm or more), the mechanicalstrength of the layer should be improved by another method.

The inorganic fine particles disclosed in Japanese Patent ProvisionalPublication No. 2000-235117 also effectively improve the mechanicalstrength of optical compensatory sheet. However, the amount of theinorganic fine particles must be so controlled that particles may notaffect the functions of the optically anisotropic layer and theorientation layer.

The applicant has further studied mechanical strength of an opticalcompensatory sheet, and succeeded in producing a sheet remarkablyimproved in mechanical strength. In preparation of the opticalcompensatory sheet, multifunctional monomers having four or more doublebonds are added into the optically anisotropic layer, and thenpolymerized. The multi-functional monomers can remarkably increase thenumber of double bonds (which serve as polymerizable functional groups)in the optically anisotropic layer without affecting the opticalfunction of the layer.

Where the number of double bonds is increased in the opticallyanisotropic layer, polymerization reaction in the layer can prepare anoptical compensatory sheet remarkably improved in mechanical strength.If the prepared optical compensatory sheet of the invention is laminatedonto a liquid crystal cell, and then peeled off, the sheet hardlybreaks, and scarcely remains on the substrate of the cell.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a sketch schematically illustrating fundamental constitutionof a liquid crystal display of transmission type.

FIG. 2 is a sketch schematically illustrating fundamental constitutionof another liquid crystal display of transmission type.

FIG. 3 is a sketch schematically illustrating fundamental constitutionof a third liquid crystal display of transmission type.

FIG. 4 is a sketch schematically illustrating fundamental constitutionof a liquid crystal display of reflection type.

DETAILED DESCRIPTION OF THE INVENTION

[Basic Structure of Liquid Crystal Display)

FIG. 1 is a sketch schematically illustrating fundamental constitutionof a liquid crystal display of transmission type.

The display shown in FIG. 1 comprises a transparent protective film (1a), a polarizing membrane (2 a), a transparent protective film (3 a, atransparent support (4 a), an optically anisotropic layer (5 a), a lowersubstrate of liquid crystal cell (6 a), rod-like liquid crystalmolecules (7), an upper substrate of liquid crystal cell (6 b), anoptically anisotropic layer (5 b), a transparent support (4 b), atransparent protective film (3 b), a polarizing membrane (2 b) and atransparent protective film (1 b), piled up in this order from the sideof a back light (BL).

A set of the transparent protective film (1 a) to the transparentprotective film (3 a) constitutes a lower polarizing plate. A set of thetransparent support (4 a) to the optically anisotropic layer (5 a)constitutes a lower optical compensatory sheet. A set of the opticallyanisotropic layer (5 b) to the transparent support (4 a) constitutes anupper optical compensatory sheet. A set of the transparent protectivefilm (3 b) to the transparent protective film (1 b) constitutes an upperpolarizing plate. If a polymer film is used both as the transparentprotective film (3 a) and the transparent support (4 a), the lowerpolarizing plate and the lower optical compensatory sheet can becombined. Also the upper optical compensatory sheet and the upperpolarizing plate can be combined if a polymer film is used both as thetransparent support (4 b) and the transparent protective film (3 b).

FIG. 2 is a sketch schematically illustrating fundamental constitutionof another liquid crystal display of transmission type.

The display shown in FIG. 2 comprises a transparent protective film (1a), a polarizing membrane (2 a), a transparent protective film (3 a), atransparent support (4), an optically anisotropic layer (5), a lowersubstrate of liquid crystal cell (6 a), rod-like liquid crystalmolecules (7), an upper substrate of liquid crystal cell (6 b), atransparent protective film (3 b), a polarizing membrane (2 b) and atransparent protective film (1 b), piled up in this order from the sideof a back light (BL).

A set of the transparent protective film (1 a) to the transparentprotective film (3 a) constitutes a lower polarizing plate. A set of thetransparent support (4) to the optically anisotropic layer (5)constitutes an optical compensatory sheet. A set of the transparentprotective film (3 b) to the transparent protective film (1 b)constitutes an upper polarizing plate. If a polymer film is used both asthe transparent protective film (3 a) and the transparent support (4),the lower polarizing plate and the optical compensatory sheet can becombined.

FIG. 3 is a sketch schematically illustrating fundamental constitutionof a third liquid-crystal display of transmission type.

The display shown in FIG. 3 comprises a transparent protective film (1a), a polarizing membrane (2 a), a transparent protective film (3 a), alower substrate of liquid crystal cell (6 a), rod-like liquid crystalmolecules (7), an upper substrate of liquid crystal cell (6 b), anoptically anisotropic layer (5), a transparent support (4), atransparent protective film (3 b), a polarizing membrane (2 b) and atransparent protective film (1 b), piled up in this order from the sideof a back light (BL).

A set of the transparent protective film (1 a) to the transparentprotective film (3 a) constitutes a lower polarizing plate. A set of theoptically anisotropic layer (5) to the transparent support (4)constitutes an optical compensatory sheet. A set of the transparentprotective film (3 b) to the transparent protective film (1 b)constitutes an upper polarizing plate. If a polymer film is used both asthe transparent support (4) and the transparent protective film (3 b),the optical compensatory sheet and the upper polarizing plate can becombined.

FIG. 4 is a sketch schematically illustrating fundamental constitutionof a liquid crystal display of reflection type.

The display shown in FIG. 4 comprises a lower substrate of liquidcrystal cell (6 a), rod-like liquid crystal molecules (7), an uppersubstrate of liquid crystal cell (6 b), an optically anisotropic layer(5), a transparent support (4), a transparent protective film (3), apolarizing membrane (2) and a transparent protective film (1), piled upin this order from the side of a reflection plate (RP).

A set of the optically anisotropic layer (5) to the transparent support(4) constitutes an optical compensatory sheet. A set of the transparentprotective film (3) to the transparent protective film (1) constitutes apolarizing plate. If a polymer film is used both as the transparentsupport (4) and the transparent protective film (3), the opticalcompensatory sheet and the polarizing plate can be combined.

[Multi-Functional Monomer]

The optically anisotropic layer comprises a cross-linked polymer. Thecross-linked polymer can comprise a main chain and a side chain thatlinks four or more positions of the main chain.

The cross-linked polymer preferably comprises a repeating unitrepresented by the formula (I):

In the formula (I), R¹ is hydrogen or an alkyl group having 1 to 6carbon atoms. R¹ preferably is hydrogen or an alkyl group having 1 to 3carbon atoms, and more preferably is hydrogen or methyl.

In the formula (I), L¹ is n-valent linking side chain. L¹ preferably isn-valent linking side chain comprising an aliphatic group, an aromaticgroup, a heterocyclic group, —O—, —S—, —CO—, —CS—, —NH— or —N<.

The aliphatic group can have a cyclic structure, a branched structure ora unsaturated bond. The aliphatic group preferably has 1 to 20 carbonatoms, more preferably has 1 to 15 carbon atoms, and most preferably has1 to 10 carbon atoms.

The aliphatic group can have a substituent group. Examples of thesubstituent groups include a halogen atom (F, Cl, Br, I), hydroxyl,carboxyl, sulfo, cyano, carbamoyl, a monovalent aromatic group, amonovalent heterocyclic group, —O—R, —CO—R, —NH—R, —N(—R)₂, —CO—O—R,—O—CO—R, —CO—NH—R, —CO—NH—R, —CO—N(—R)₂ and —NH—CO—R. R is a monovalentaliphatic group, a monovalent aromatic group or a monovalentheterocyclic group. Carboxyl and sulfo can be dissociated or can form asalt.

The aromatic group preferably has a benzene ring or a naphthalene ring.

The aromatic group can have a substituent group. Examples of thesubstituent groups include a halogen atom (F, Cl, Br, I), hydroxyl,carboxyl, sulfo, cyano, carbamoyl, a monovalent aliphatic group, amonovalent aromatic group, a monovalent heterocyclic group, —O—R, —CO—R,—NH—R, —N(—R)₂, —CO—O—R, —O—CO—R, —CO—NH—R, —CO—N(—R)₂ and —NH—CO—R. Ris a monovalent aliphatic group, a monovalent aromatic group or amonovalent heterocyclic group. Carboxyl and sulfo can be dissociated orcan form a salt.

The heterocyclic group preferably has three-membered to seven-memberedring. The heterocyclic group can have an unsaturated bond. Theheterocyclic group can have a substituent group. Examples of thesubstituent groups are the same as those of the aromatic group.

In the formula (I), n is an integer of 4 or more.

The cross-linked polymer is formed from multi-functional monomers havingfour or more double bonds. The double bond is preferably ethylenically(aliphatic) unsaturated.

The number of double bonds contained in one monomer is preferably in therange of 4 to 20, more preferably in the range of 5 to 15, and mostpreferably in the range of 6 to 10.

The multi-functional monomer is preferably an ester of a polyol havingfour or more hydroxyl groups with an unsaturated fatty acid. Examples ofthe unsaturated fatty acids include acrylic acid, methacrylic acid,maleic acid and itaconic acid. Acrylic acid and methacrylic acid arepreferred.

The polyol having four or more hydroxyl groups preferably is apolyhydric alcohol having four or more hydroxyl groups or an oligomer ofpolyhydric alcohols having three or more hydroxyl groups. The oligomerhas a structure in which polyhydric alcohols are combined with etherlinkage, ester linkage or urethane linkage (preferably, with etherlinkage).

Examples of the esters of polyol with (meth) acrylic acid includepentaerythritol tetra(meth) acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth) acrylate, poly(meth) acrylate ofpolyether polyol, poly(meth) acrylate of polyester polyol and poly(meth)acrylate of polyurethane polyol.

Multi-functional monomers are commercially available. Examples of thecommercially available monomers include Diabeam UK-4154 (MitsubishiRayon Co., Ltd.), Aronics M450 (Toa Gosei Co., Ltd.) and KAYARAD/DPHA,SR355 (Nippon Kayaku Co., Ltd.).

Two or more monomers can be used in combination.

The multi-functional monomers having four or more double bonds can beused in combination with other monomers having one to three doublebonds. It is effective in controlling the viscosity and the mechanicalstrength to use the monomers in combination. The intermolecularinteraction increases in proportion to the number of double bonds in themonomers, and accordingly the viscosity increases. When the viscosityincreases, it takes relatively long time to align the liquid crystalmolecules. On the other hand, the more double bonds the monomers have,the more the mechanical strength is improved. If the monomers are usedin combination, proper viscosity and satisfying mechanical strength canbe easily obtained.

The multi-functional monomers having four or more double bonds are usedpreferably in an amount of 20 to 80 wt. %, and more preferably in anamount of 30 to 70 wt. % based on the total amount of monomer.

The multi-functional monomers and the liquid crystal molecules are addedin combination into the optically anisotropic layer. The amount of themulti-functional monomers is preferably in the range of 0.1 to 50 wt. %,and more preferably in the range of 1 to 20 wt. % based on the amount ofthe liquid crystal molecules.

[Transparent Support]

The term “transparent” means that light transmittance is not less than80%.

The retardation values in plane (Re) and along the thickness direction(Rth) of the transparent film are in the ranges of 0 to 50 nm and 70 to400 nm, respectively. They are defined by the following formulas (II)and (III), respectively:Re=(nx−ny)×d   (II)Rth=[{(nx+ny)/2}−nz]×d.   (III)

In the formulas (II) and (III), nx is a refractive index along the slowaxis (direction giving the maximum refractive index) in the plane of thesupport.

In the formulas (II) and (III), ny is a refractive index along the fastaxis (direction giving the minimum refractive index) in the plane of thesupport.

In the formula (III), nz is a refractive index along the thicknessdirection of the support.

In the formulas (II) and (III), d is the thickness of the support interms of nm.

If two optical compensatory sheets are installed in a liquid crystalcell, the transparent support preferably has a Rth retardation value inthe range of 70 to 200 nm.

If one optical compensatory sheets is installed in a liquid crystalcell, the transparent support preferably has a Rth retardation value inthe range of 150 to 400 nm.

The transparent support preferably has birefringent indexes in plane(An: nx-ny) and along the thickness direction ({(nx+ny)/2}−nz) in theranges of less than 0.002 and 0.001 to 0.04, respectively.

The transparent support is preferably a film of polymer. The polymer ispreferably cellulose ester, more preferably cellulose acetate, andfurther preferably cellulose acetate having an acetic acid content inthe range of 59.0 to 61.5 %. The term “acetic acid content” means theweight ratio of the combined acetic acid based on the amount of thecellulose unit. The acetic acid content can be measured and calculatedaccording to ASTM, D-817-91 (Testing methods for cellulose acetateetc.).

The polymer for the support preferably has a viscosity average degree ofpolymerization (DP) of not less than 250, and more preferably not lessthan 290. Further, the polymer preferably has a narrow molecular weightdistribution in terms of Mw/Mn (wherein Mw means the weight averagemolecular weight, and Mn means the number average molecular weight),which can be measured by a gel permeation chromatography. The value ofMw/Mn is preferably in the range of 1.0 to 1.7, more preferably in therange of 1.30 to 1.65, and most preferably in the range of 1.40 to 1.60.

For controlling the retardation of the polymer film, an aromaticcompound having at least two aromatic rings can be used as a retardationincreasing agent.

If a cellulose acetate film is used as the polymer film, the aromaticcompound is added in an amount of 0.01 to 20 weight parts, preferably inan amount of 0.05 to 15 weight parts, more preferably in an amount of0.1 to 10 weight parts, based on 100 weight parts of cellulose acetate.Two or more aromatic compounds may be used in combination.

In the present invention, ‘an aromatic ring’ means not only an aromatichydrocarbon ring but also an aromatic heterocyclic ring.

As the aromatic hydrocarbon ring, a six-membered ring (namely, a benzenering) is preferred.

The aromatic heterocyclic ring is generally unsaturated. The aromaticheterocyclic ring is preferably a five-, six- or seven-membered ring,and more preferably a five- or six-membered ring. The aromaticheterocyclic ring generally has double bonds as many as possible. Thehetero-atom in the ring preferably is nitrogen atom, sulfur atom oroxygen atom, and more preferably is nitrogen atom. Examples of thearomatic heterocyclic ring include furan ring, thiophene ring, pyrrolering, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring,imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring,pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring and1,3,5-triazine ring.

Preferred aromatic rings are benzene ring, furan ring, thiophene ring,pyrrole ring, oxazole ring, thiazole ring, triazole ring, pyridine ring,pyrimidine ring, pyrazine ring and 1,3,5-triazine ring. Benzene ring and1,3,5-triazine ring are more preferred

The aromatic compound preferably contains at least one 1,3,5-triazinering.

The number of aromatic rings in the aromatic compound is preferably inthe range of 2 to 20, more preferably in the range of 2 to 12, furtherpreferably in the range of 2 to 8, and most preferably in the range of 2to 6.

The relation of the two or more aromatic rings is categorized into threecases, namely

(a) the case in which the aromatic rings form a condensed ring,

(b) the case in which the aromatic rings are connected through a singlebond, and

(c) the case in which the aromatic rings are connected through a linkinggroup.

In case (c), a spiro-bonding is not formed because the rings arearomatic.

The relation of the aromatic rings may be any of the cases (a) to (c).

Examples of the condensed ring in the case (a) include indene ring,naphthalene ring, azulene ring, fluorene ring, phenanthrene ring,anthracene ring, acenaphthylene ring, naphthacene ring, pyrene ring,indole ring, isoindole ring, benzofuran ring, benzothiophene ring,indolizine ring, benzoxazole ring, benzothiazole ring, benzimidazolering, benztriazole ring, purine ring, indazole ring, chromene ring,quinoline ring, isoquinoline ring, quinolizine ring, quinazoline ring,cinnoline ring, quinoxaline ring, phthalazine ring, pteridine ring,carbazole ring, acridine ring, phenanthridine ring, xanthene ring,phenazine ring, phenothiazine ring, phenoxthine ring, phenoxazine ringand thianthrene ring. Preferred are naphthalene ring, azulene ring,indole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring,benztriazole ring and quinoline ring.

The single bond in the case (b) is preferably between carbon atoms ofthe two aromatic rings. Two or more single bonds may connect the twoaromatic rings to form an aliphatic ring or a non-aromatic ring betweenthem.

The linking group in the case (c) is also preferably between carbonatoms of the two aromatic rings. The linking group is preferably analkylene group, an alkenylene group, an alkynylene group, —CO—, —O—,—NH—, —S— and a combination thereof.

Examples of the linking group formed by the combination are shown below.In each of the following examples, the right and left terminals may bereversed.

c1: —CO—O—

c2: —CO—NH—

c3: -alkylene-O—

c4: —NH—CO—NH—

c5: —NH—CO—O—

c6: —O—CO—O—

c7: —O-alkylene-O—

c8: —CO-alkenylene-

c9: —CO-alkenylene-NH—

c10: —CO-alkenylene-O—

c11: -alkylene-CO—O-alkylene-O—CO-alkylene-

c12: —O-alkylene-CO—O-alkylene-O—CO-alkylene-O—

c13: —O—CO-alkylene-CO—O—

c14: —NH—CO-alkenylene-

c15: —O—CO-alkenylene-

The aromatic ring and the linking group may have substituent groups.

Examples of the substituent group include halogen atoms (F, Cl, Br, I),hydroxyl, carboxyl, cyano, amino, nitro, sulfo, carbamoyl, sulfamoyl,ureido, an alkyl group, an alkenyl group, an alkynyl group, an aliphaticacyl group, an aliphatic acyloxy group, an alkoxy group, analkoxycarbonyl group, an alkoxycarbonylamino group, an alkylthio group,an alkylsulfonyl group, an aliphatic amido group, an aliphaticsulfonamido group, an aliphatic substituted amino group, an aliphaticsubstituted carbamoyl group, an aliphatic substituted sulfamoyl group,an aliphatic substituted ureido group and a non-aromatic heterocyclicgroup.

The alkyl group preferably has 1 to 8 carbon atoms. A chain alkyl groupis preferred to a cyclic one, and a straight chain alkyl group isparticularly preferred. The alkyl group may further have a substituentgroup (e.g., hydroxyl, carboxyl, an alkoxy group, an alkyl-substitutedamino group). Examples of the (substituted) alkyl group include methyl,ethyl, n-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyland 2-diethylaminoethyl.

The alkenyl group preferably has 2 to 8 carbon atoms. A chain alkenylgroup is preferred to a cyclic one, and a straight chain alkenyl groupis particularly preferred. The alkenyl group may further have asusbstituent group. Examples of the alkenyl group include vinyl, allyland 1-hexenyl.

The alkynyl group preferably has 2 to 8 carbon atoms. A chain alkynylgroup is preferred to a cyclic one, and a straight chain alkynyl groupis particularly preferred. The alkynyl group may further have asusbstituent group. Examples of the alkynyl group include ethynyl,1-butynyl and 1-hexynyl.

The aliphatic acyl group preferably has 1 to 10 carbon atoms. Examplesof the aliphatic acyl group include acetyl, propanoyl and butanoyl.

The aliphatic acyloxy group preferably has 1 to 10 carbon atoms.Examples of the aliphatic acyloxy group include acetoxy.

The alkoxy group preferably has 1 to 8 carbon atoms. The alkoxy groupmay further have a susbstituent group (e.g., another alkoxy group).Examples of the (substituted) alkoxy group include methoxy, ethoxy,butoxy and methoxyethoxy.

The alkoxycarbonyl group preferably has 2 to 10 carbon atoms. Examplesof the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl.

The alkoxycarbonylamino group preferably has 2 to 10 carbon atoms.Examples of the alkoxycarbonylamino group include methoxycarbonylaminoand ethoxycarbonylamino.

The alkylthio group preferably has 1 to 12 carbon atoms. Examples of thealkylthio group include methylthio, ethylthio and octylthio.

The alkylsulfonyl group preferably has 1 to 8 carbon atoms. Examples ofthe alkylsulfonyl group include methanesulfonyl and ethanesulfonyl.

The aliphatic amido group preferably has 1 to 10 carbon atoms. Examplesof the aliphatic amido group include acetoamido.

The aliphatic sulfonamido group preferably has 1 to 8 carbon atoms.Examples of the aliphatic sulfonamido group include methanesulfonamido,butanesulfonamido and n-octanesulfonamido.

The aliphatic substituted amine group preferably has 1 to 10 carbonatoms. Examples of the aliphatic substituted amine group includedimethylamino, diethylamino and 2-carboxyethyl amino.

The aliphatic substituted carbamoyl group preferably has 2 to 10 carbonatoms. Examples of the aliphatic substituted carbamoyl group includemethylcarbamoyl and diethylcarbamoyl.

The aliphatic substituted sulfamoyl group preferably has 1 to 8 carbonatoms. Examples of the aliphatic substituted sulfamoyl group includemethylsulfamoyl and diethylsulfamoyl.

The aliphatic substituted ureido group preferably has 2 to 10 carbonatoms. Examples of the aliphatic substituted ureido group includemethylureido.

Examples of the non-aromatic heterocyclic group include piperidino andmorpholino.

The retardation increasing agent has a molecular weight of 300 to 800.

Concrete examples of the retardation increasing agent are described inJapanese Patent Provisional Publication Nos. 2000-111014, 2000-275434and International Patent Application No. WO00/65384.

The polymer film is preferably prepared according to a solvent castingmethod. The solvent casting method comprises the steps of dissolvingcellulose ester in an organic solvent to prepare a solution (dope) andcasting the dope to prepare a film.

The organic solvent is preferably selected from the group consisting ofan ether having 3 to 12 carbon atoms, a ketone having 3 to 12 carbonatoms, an ester having 3 to 12 carbon atoms and a halogenatedhydrocarbon having 1 to 6 carbon atoms.

The ether, ketone and ester may have a cyclic structure. A compoundhaving two or more functional groups of the ether (—O—), ketone (—CO—)and ester (—COO—) can also be used as the organic solvent. The organicsolvent can have another functional group such as alcoholic hydroxyl. Inthe case where the organic solvent has two or more functional group, thenumber of the carbon atoms is defined as a compound having onefunctional group, which is optionally selected from the group of theorganic solvents.

Examples of the ethers having 3 to 12 carbon atoms include diisopropylether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane,tetrahydrofuran, anisole and phenetol.

Examples of the ketones having 3 to 12 carbon atom include acetone,methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanoneand methylcyclohexanone.

Examples of the esters having 3 to 12 carbon atoms include ethylformate, propyl formate, pentyl formate, methyl acetate, ethyl acetateand pentyl acetate.

Examples of the compounds having two or more kinds of functional groupsinclude 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

The halogenated hydrocarbon preferably has one or two carbon atoms, andmore preferably has one carbon atom. The halogen atom of the halogenatedhydrocarbon preferably is chlorine. The ratio of the substitution ofhydrogen with halogen is preferably in the range of 25 to 75 mole %,more preferably in the range of 30 to 70 mole %, further preferably inthe range of 35 to 65 mole %, and most preferably in the range of 40 to60 mole %. Methylene chloride is a representative halogenatedhydrocarbon.

Two or more organic solvents can be used in combination.

A polymer solution can be prepared according to a conventional method.The conventional method means that the solution is prepared at atemperature of not lower than 0° C. (ordinary or elevated temperature).The preparation of the solution can be conducted by using a process andapparatus for preparation of a dope in a conventional solvent castingmethod. The conventional method preferably uses a halogenatedhydrocarbon (particularly methylene chloride) as an organic solvent.

The amount of the polymer is so adjusted that a prepared solutioncontains cellulose ester in an amount of 10 to 40 wt. %. The amount ofcellulose ester more preferably is 10 to 30 wt. %. An optional additive(described below) can be added to an organic solvent.

The solution can be prepared by stirring the polymer and an organicsolvent at an ordinary temperature (0 to 40° C.). A solution of a highconcentration is preferably prepared by stirring them at an elevatedtemperature and at a high pressure. In that case, the polymer and theorganic solvent are placed in a closed vessel, and are stirred at anelevated temperature and at a high pressure. The temperature is set tobe higher than the boiling point at atmospheric pressure but lower thanthe boiling point of the solvent at the high pressure. In concrete, theheating temperature is usually not lower than 40° C., preferably in therange of 60 to 200° C., and more preferably in the range of 80 to 1100C.

The components can be preliminary dispersed coarsely, and the coarsedispersion can be placed in the vessel. Otherwise, the components canalso be introduced into the vessel in series. The vessel should beequipped with a stirring device. A pressure in the vessel can be formedby introducing an inert gas such as nitrogen gas into the vessel, or byheating and evaporating the solvent to increase the vapor pressure.Further, the components can be added to the vessel at a high pressureafter the vessel is sealed.

The vessel is preferably heated outside. For example, the vessel can beheated by a jacket type heating apparatus. Further, a plate heater canbe placed outside the vessel. Furthermore, a heated liquid can becirculated in a tube outside the vessel.

The components are stirred preferably by a stirring wing placed in thevessel. The stirring wing has such a length that the end of the wingreaches near the wall of the vessel. A scratching wing is preferablyattached to the end of the stirring wing to scratch the solutionremaining on the wall of the vessel.

The vessel can have a meter such as a manometer or a thermometer. Thecomponents are dissolved in the solvent in the vessel. The prepared dopeis cooled in the vessel, or the dope is cooled after it is taken out ofthe vessel. The dope can be cooled by a heat exchanger.

The solution can be also prepared according to a cooling dissolutionmethod. According to the cooling dissolution method, the polymer can bedissolved even in organic solvents in which the polymer cannot bedissolved according to a conventional method. Further, if organicsolvents in which the polymer can be dissolved according to aconventional method are used, the cooling dissolution method can preparea solution more quickly.

At the first stage of the cooling dissolution method, the polymer isgradually added to an organic solvent while stirring at roomtemperature.

The amount of the polymer is in the range of 10 to 40 wt. % based on theamount of the mixture, and is preferably in the range of 10 to 30 wt. %.An optional additive (described below) may be added to the mixture.

At the next stage, the mixture is cooled to a temperature of −100 to−10° C., preferably −80 to −10° C., more preferably −50 to −20° C., andmost preferably −50 to −30° C. The mixture can be cooled in a dryice/methanol bath (−75° C.) or in a cooled diethylene glycol solution(−30 to −20° C.). At the cooling stage, the mixture of the polymer andthe solvent generally solidify.

The cooling rate is preferably faster than 4° C. per minute, morepreferably faster than 8° C. per minute, and most preferably faster than12° C. per minute. The cooling rate is preferably as fast as possible.However, a theoretical upper limit of the cooling rate is 10,000° C. persecond, a technical upper limit is 1,000° C. per second, and a practicalupper limit is 100° C. per second. The cooling rate means the change oftemperature at the cooling stage per the time taken to complete thecooling stage. The change of temperature means the difference betweenthe temperature at which the cooling stage is started and thetemperature at which the cooling stage is completed.

The solidified mixture is warmed to a temperature of 0 to 200° C.,preferably 0 to 150° C., more preferably 0 to 120° C., and mostpreferably 0 to 50° C. to dissolve the cellulose ester in the solvent.The mixture can be warmed by keeping it at room temperature or on a hotbath.

The warming rate is preferably faster than 4° C. per minute, morepreferably faster than 8° C. per minute, and most preferably faster than12° C. per minute. The warming rate is preferably fast as possible.However, a theoretical upper limit of the warming rate is 10,000° C. persecond, a technical upper limit is 1,000° C. per second, and a practicalupper limit is 100° C. per second. The warming rate means the change oftemperature at the warming stage per the time taken to complete thewarming stage. The change of temperature means the difference betweenthe temperature at which the warming stage is started and thetemperature at which the warming stage is completed.

Thus a dope is formed as a uniform solution. If the polymer is notsufficiently dissolved, the cooling and warming steps can be repeated.The dope is observed with eyes to determine whether the polymer issufficiently dissolved or not.

A sealed vessel is preferably used in the cooling dissolution method toprevent contamination of water, which is caused by dew condensation atthe cooling step. The time for the cooling and warming stages can beshortened by conducting the cooling step at a high pressure andconducting the warming step at a low pressure. A pressure vessel ispreferably used at a high or low pressure.

In the case that cellulose acetate having acetic acid content of 60.9%and viscosity average polymerization degree of 299 is dissolved inmethyl acetate by a cooling dissolution method to form 20 wt. %solution, the solution has a pseudo sol-gel phase transition point atabout 33° C., which is measured by differential scanning calorimetricanalysis (DSC). Under the transition point, the solution forms a uniformgel. Therefore, the solution should be stored at a temperature higherthan the transition point, preferably at a temperature about 10° C.higher than the point. The pseudo sol-gel phase transition point dependson the combined average acetic acid content of cellulose acetate, theviscosity average degree of polymerization, the concentration of thedope and the nature of the solvent.

From the obtained polymer solution (dope), a polymer film is preparedaccording to a solvent casting method. The above-described retardationincreasing agent is preferably added to the dope.

The dope is cast on a drum or a band, and then evaporated to form apolymer film.

Before casting the dope, the concentration of the dope is so adjustedthat the solid content of the dope is in the range of 18 to 35 wt. %.The surface of the drum or band is preferably polished to give a mirrorplane. The casting and drying stages of the solvent cast methods aredescribed in U.S. Pat. Nos. 2,336,310, 2,367,603, 2,492,078, 2,492,977,2,492,978, 2,607,704, 2,739,069, 2,739,070, British Patent Nos. 640,731,736,892, Japanese Patent Publication Nos. 45(1970)-4554, 49(1974)-5614,Japanese Patent Provisional Publication Nos. 60(1985)-176834,60(1985)-203430 and 62(1987)-115035.

The drum or band preferably has a surface temperature of not higher than10° C. when the dope is cast on the support. After casting the dope, thedope is preferably dried with flowing air for at least 2 seconds. Theformed film is peeled off the drum or band, and the film can be furtherdried with hot air to remove the solvent remaining in the film. Thetemperature of the air can be gradually elevated from 100 to 160° C. Theabove-mentioned method is described in Japanese Patent Publication No.5(1993)-17844. According to the method, the time for casting and peelingsteps can be shortened. The method requires that the dope be set to gelat the surface temperature of the drum or band. The dope formedaccording to the present invention satisfies the requirement.

A film having two or more layers can be formed by simultaneously casting(co-casting) the dopes. Before casting the dopes, the concentration ofeach dope is so adjusted that the solid content is in the range of 10 to50 wt. %.

In the case where two or more cellulose acetate solutions are used, thesolutions may be cast from nozzles provided at intervals in thetransferring direction of the support to form a layered film. Thismethod is described in, for example, Japanese Patent ProvisionalPublication Nos. 61(1986)-158414, 1(1989)-122419 and 11(1999)-198285.The solutions may be simultaneously cast from two nozzles to form alayered film. This method is described in, for example, Japanese PatentPublication No. 60(1985)-27562, Japanese Patent Provisional PublicationNos. 61(1986)-94724, 61(1986)-947245, 61(1986)-104813, 61(1986)-158413and 6(1994)-134933.

The method described in Japanese Patent Provisional Publication No.56(1981)-162617 can be also adopted. In that method, a highly viscouspolymer solution is enclosed with a low viscous one, and then thethus-combined solutions are simultaneously extruded and cast.

Further, the method described in, for example, Japanese PatentPublication No. 44(1969)-20235 may be adopted. In the method, a film isbeforehand formed from a solution extruded out of one of two nozzles.After the formed film is peeled and reversely placed on the support,another solution is extruded from the other nozzle to cast onto the film(on the surface having faced to the support) to form a layered film.

The polymer solutions may be the same or different from each other.Besides a polymer film for the transparent support, other functionallayers (e.g., adhesive layer, dye layer, antistatic layer, anti-halationlayer, ultraviolet layer, polarizing layer) can be also formed bysimultaneous casting.

In the case where a film having a single layer is formed by the solventcasting method, it is necessary to extrude a dope of high concentrationand high viscosity. That dope is generally so unstable that solidparticles are often deposited and that the formed film often has poorevenness. If such viscous dope is extruded simultaneously from pluralnozzles onto the support, a film having excellent evenness can beprepared. Further, since the thick dope is rapidly dried, the film canbe rapidly produced.

A plasticizer can be added to the polymer film to improve the mechanicalstrength of the film. The plasticizer has another function of shorteningthe time for the drying process. Phosphoric esters and carboxylic estersare usually used as the plasticizer. Examples of the phosphoric estersinclude triphenyl phosphate (TPP) and tricresyl phosphate (TCP).Examples of the carboxylic esters include phthalic esters and citricesters. Examples of the phthalic esters include dimethyl phthalate(DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctylphthalate (DOP), diphenyl phthalate (DPP) and diethylhexyl phthalate(DEHP). Examples of the citric esters include triethyl o-acetylcitrate(OACTE) and tributyl o-acetylcitrate (OACTB). Examples of the othercarboxylic esters include butyl oleate, methylacetyl ricinoleate,dibutyl sebacate and various trimellitic esters. Phthalic esterplasticizers (DMP, DEP, DBP, DOP, DPP, DEHP) are preferred. DEP and DPPare particularly preferred.

The amount of the plasticizer is preferably in the range of 0.1 to 25wt. %, more preferably in the range of 1 to 20 wt. %, and mostpreferably in the range of 3 to 15 wt. % based on the amount of thepolymer.

Deterioration inhibitors (e.g., antioxidizing agent, peroxidedecomposer, radical inhibitor, metal inactivating agent, oxygenscavenger, amine) can be incorporated into the polymer film. Thedeterioration inhibitors are described in Japanese Patent ProvisionalPublication Nos. 3(1991)-199201, 5(1993)-1907073, 5(1993)-194789,5(1993)-271471 and 6(1994)-107854. The deterioration inhibitor ispreferably added in the range of 0.01 to 1 wt. %, and more preferably inthe range of 0.01 to 0.2 wt. % based on the amount of the preparedsolution (dope). If the amount is less than 0.01 wt. %, the effect ofthe deterioration inhibitor can not be expected. If the amount is morethan 1 wt. %, the inhibitor would bleed out on the surface of the film.Butyrated hydroxytoluene (BHT) and tribenzylamine (TBA) are particularlypreferred deterioration inhibitors.

For improving thermal conductivity of the transparent support, varioushighly thermal conductive particles can be added to the polymer film.The thermal conductive particles are preferably made of transparentmaterial. Examples of the material include aluminum nitride, siliconnitride, boron nitride, magnesium nitride, silicon carbide, aluminumoxide, silicon oxide, zinc oxide, magnesium oxide, carbon (includingdiamond) and metals.

The highly thermal conductive particles have a mean particle sizepreferably in the range of 0.05 to 80 μm, more preferably in the rangeof 0.1 to 10 μm.

The amount of the thermal conductive particles is preferably in therange of 5 to 100 weight parts, more preferably in the range of 5 to 50weight parts based on 100 weight parts of the polymer.

For preventing the polymer film from being swollen with moisture (forreducing the moisture swelling coefficient of the polymer film), thefilm is preferably stretched. The stretching is preferably performed sothat distortions in all the directions in plane may be evenly inhibited,and hence biaxial stretching is preferred.

In the biaxial stretching, the film is simultaneously or successivelystretched in two directions (namely, simultaneous biaxial stretching orsuccessive biaxial stretching). The successive biaxial stretching ispreferred in consideration of continuous production. The process of thesuccessive biaxial stretching comprises the steps of casting the dope,peeling the formed film from the band or drum, stretching the filmlaterally (perpendicularly to the casting direction), and thenstretching the film longitudinally. The longitudinal stretching step maybe performed prior to the lateral stretching.

Japanese Patent Provisional Publication Nos. 62(1987)-115035,4(1992)-152125, 4(1992)-284211, 4(1992)-298310 and 11(1999)-48271describe the lateral stretching, which is performed at room temperatureor an elevated temperature. The elevated temperature is preferably belowthe glass transition point of the film. The film can be stretched whilebeing dried in the film production. Preferably, the film is stretchedwhile the solvent still remains in the film. The longitudinal stretchingcan be performed, for example, by controlling the conveying rollers sothat the speed of winding up the film may be faster than that of peelingthe film. The lateral stretching, on the other hand, can be performed bygradually widening the interval between tenters clipping both sides ofthe conveyed film. Otherwise, after the film is dried, it can bestretched by means of a stretching machine (preferably, the film ismonoaxially stretched by means of a long stretching machine). Theexpanding ratio of stretching (the ratio of length increased bystretching based on the original length) is preferably in the range of 5to 50%, more preferably in the range of 10 to 40%, most preferably inthe range of 15 to 35%.

The steps from casting to drying may be performed under relatively inertatmosphere (e.g., nitrogen gas atmosphere). For winding up the film,generally used machines can be used. Examples of the winding methodinclude constant tension method, constant torque method, taper tensionmethod and programmed tension control method by which inner stress iskept constant.

By the above-described biaxial stretching, the moisture swellingcoefficient of the polymer film can be reduced. The moisture swellingcoefficient is determined by measuring the change of length of thesample when the relative humidity is changed with the temperature keptconstant.

In order not to unevenly increase the transmittance at the peripheralarea of the film, the cellulose acetate film has a moisture swellingcoefficient of preferably 30×10⁻⁵/% RH or less, more preferably15×10⁻⁵/% RH or less, most preferably 10×10⁻⁵/% RH or less. The less themoisture swelling coefficient is, the more it is preferred. However, itis usually 1.0×10^(×5)/% RH or more.

The moisture swelling coefficient is determined in the following manner.First, the formed polymer film is cut to prepare a sample (5 mm width×20mm length). The end of the sample is fixed, and the sample is suspendedat 25° C., 20% RH (R₀). At the free end of the sample, a weight of 0.5 gis further suspended. After 10 minutes, the length of the sample (L₀) ismeasured. The humidity is then changed to 80% RH (R₁) while thetemperature is kept at 25° C., and the length (L₁) is measured again.From the measured values, the moisture swelling coefficient iscalculated according to the following formula. Ten samples are preparedfrom the same film, and the procedure is repeated. The calculated valuesare averaged to determine the moisture swelling coefficient.Moisture swelling coefficient [/% RH]={(L₁−L₀)/L₀}/(R₁−R₀)

The less free volume the polymer film has, the less the size of the filmis changed with moisture. The free volume depends upon the amount ofremaining solvent used in film forming process. The less the solventremains, the less the size changes.

For reducing the remaining solvent, the film is dried at a hightemperature for long time. However, if too much time is spent fordrying, the productivity is lowered. Accordingly, the amount ofremaining solvent is preferably in the range of 0.01 to 1 wt. %, morepreferably in the range of 0.02 to 0.07 wt. %, most preferably in therange of 0.03 to 0.05 wt. %.

The amount of remaining solvent is so controlled that the polymer filmmay be produced at a low cost with high productivity.

As another method for reducing the film-size change with moisture, acompound having hydrophobic groups is preferably added. Preferredexamples of the hydrophobic groups include alkyl groups and phenyl. Thecompound is preferably selected from the plasticizers or thedeterioration inhibitors which can be added in to the polymer film.Examples of the compound include triphenyl phosphate (TPP) andtribenzylamine (TBA).

The amount of the compound having hydrophobic groups is preferably inthe range of 0.01 to 10 wt. %, more preferably in the range of 0.1 to 5wt. %, most preferably in the range of 1 to 3 wt. %.

The polymer film is preferably subjected to a surface treatment.Examples of the surface treatment include corona discharge treatment,glow discharge treatment, flame treatment, alkali saponificationtreatment and ultraviolet (UV) treatment. In place of the surfacetreatment, an undercoating layer (described in Japanese PatentProvisional Publication No. 7(1995)-333433) may be provided.

The film after the surface treatment has a surface energy preferably inthe range of not more than 55 mN/m, more preferably in the range of 60to 75 mN/m.

For ensuring the evenness of the film, the surface treatment ispreferably performed so that the temperature of the film may be nothigher than Tg (glass transition temperature) of the film (namely, nothigher than 150° C.).

In the case where the polymer film is a cellulose acetate film, the filmis preferably subjected to acid or alkali treatment. This means thecellulose acetate film is preferably subjected to saponificationtreatment (particularly preferably, alkali saponification treatment).

The alkali saponification treatment can be cyclically performed by thesteps of immersing the film in an alkali solution, washing with waterand drying. Before washing, the film may be neutralized with an acidicsolution. Examples of the alkali solution include aqueous solutions ofpotassium hydroxide and sodium hydroxide. The normality of hydroxyl ionin the alkali solution is preferably in the range of 0.1 to 3.0 N, morepreferably in the range of 0.5 to 2.0 N. The alkali solution is kept ata temperature preferably in the range of 0 to 90° C., more preferably inthe range of 40 to 70° C.

For efficiently saponifying the film, it is also preferred to apply analkali solution onto the cellulose acetate film. After thesaponification, the film is preferably washed to remove the alkalisolution from the surface. If the saponification is performed byapplying, the alkali solution preferably has good wettability onto thecellulose acetate film. The wettability of the solution mainly dependsof what kind of solvent is used. Examples of the solvent giving goodwettability include alcohols (e.g., isopropyl alcohol, n-butanol,methanol, ethanol). As an auxiliary solvent, water or glycol (e.g.,propylene glycol, ethylene glycol) is preferably added.

The surface energy can be measured by the contact angle method, the wetheating method or the adsorption method (these methods are described in‘The basic theory and application of wetting (written in Japanese)’,published by Realize Co., Ltd, 1989). The contact angle method ispreferred. In that method, two solutions having known surface energiesare dropped onto the film. The contact angle of each drop is measured,and the surface energy of the film is calculated from the measuredcontact angles. The contact angle is, by definition, an angle (includingthe drop) between the film surface and the tangent of the drop surfaceat their crossing point.

[Orientation Layer]

An orientation layer has a function for aligning the liquid crystalmolecules.

The orientation layer can be formed by rubbing treatment of an organiccompound (preferably a polymer), oblique evaporation of an inorganiccompound, formation of a micro groove layer, or stimulation of anorganic compound (e.g., ω-tricosanoic acid, dioctadecylmethylammoniumchloride, methyl stearate) according to a Langmuir-Blodgett method.Further, the aligning function of the orientation layer can be activatedby applying an electric or magnetic field to the layer or irradiatingthe layer with light.

The orientation layer is preferably formed by rubbing a polymer. Thepolymer for orientation layer generally has a molecular structure foraligning the liquid crystal molecules.

Besides the function of aligning the liquid crystal molecules, thepolymer for the orientation layer in the invention preferably has amolecular structure in which a side chain having cross-linkablefunctional groups (e.g., double bonds) is connected to the main chain.The side chain can also have a group having the function of aligning theliquid crystal molecules.

Examples of the main chain of the polymer for orientation layer includepolyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyacrylicesters, polymrthacrylic esters (e.g., polymethyl methacrylate),polyacrylamide (e.g., poly(N-methylol acrylamide) ), polymethacrylamide,polyolefin (e.g., polystyrene, polyvinyltoluene, polyethylene,polypropylene). chlorinated polyolefin (e.g., chlorosulfonatedpolyethylene, polyvinyl chloride), cellulose ester (e.g., cellulosenitrate), polyester (e.g., polycarbonate), polyimide, polyamide (e.g.,polyamic acid), polyvinyl ester (e.g., polyvinyl acetate) and celluloseether (e.g., carboxymethylcellulose). Copolymers comprising two or morekinds of repeating units (e.g., acrylic acid/methacrylic acid copolymer,styrene/maleinimide copolymer, styrene/vinyltoluene copolymer, vinylacetate/vinyl chloride copolymer, ethylene/vinyl acetate copolymer) arealso usable. Further, reaction products of silane coupling agents can bealso used as the polymer for the orientation layer.

Poly(N-methylol acrylamide), carboxymethylcellulose, polyvinyl alcohol,polyacrylic acid, polymethacrylic acid, polyimide and polyamide arepreferred, and polyvinyl alcohol is particularly preferred.

The saponification degree of polyvinyl alcohol is preferably in therange of 70 to 100%, more preferably in the range of 80 to 100%, mostpreferably in the range of 85 to 95%. The polymerization degree ofpolyvinyl alcohol is preferably in the range of 100 to 3,000.

The side chain having the function of aligning the liquid crystalmolecules generally has hydrophobic groups as functional groups, whichare determined according to the liquid crystal molecules and thealigning mode.

In order that the polymer for orientation layer and the multi-functionalmonomers in the optically anisotropic layer are copolymerized, thepolymer has a structure in which the side chain having cross-linkablefunctional groups is connected to the main chain, or in which thecross-linkable groups is introduced to the side chain having thefunction of aligning the liquid crystal molecules. As a result, strongcovalent bonds are formed not only among the multi-functional monomersbut also in the polymer for the orientation layer and between thepolymer and the multi-functional monomers. Consequently, the mechanicalstrength of optical compensatory sheet can be remarkably improved byintroducing the cross-linkable functional groups into the polymer fororientation layer.

As the multi-functional monomer preferably does, the cross-linkablefunctional group introduced into the polymer also preferably has adouble bond. Examples of the cross-linkable functional group having adouble bond are shown below.

The cross-linkable functional group may be connected to the main chainof the polymer for orientation layer either directly or via a linkinggroup.

The linking group is preferably a divalent linking group selected fromthe group consisting of an alkylene group, an arylene group, —CO—, —NH—,—O—, —S— and combinations thereof. The alkylene group preferably has 1to 12 carbon atoms. The arylene group is preferably phenylene.

The polymer for orientation layer (particularly, the polymer having amain chain of polyvinyl alcohol) can be cross-linked by a cross-linkingagent besides the above-described cross-linkable functional groups.

Examples of the cross-linking agent include aldehydes, N-methylolcompounds, dioxane derivatives, compounds that works when the carboxylicgroup is activated, active vinyl compounds, active halogen compounds,isooxazoles and dialdehyde starch. Examples of the aldehydes includeformaldehyde, glyoxal and glutaraldehyde. Examples of the N-methylolcompounds include dimethylol urea and methyloldimethylhydantoin.Examples of the dioxane derivatives include 2,3-dihydroxydioxane.Examples of the compounds that works when the carboxylic group isactivated include carbenium, 2-naphthalenesulfonate,1,1-bispyrrolidino-1-chloropyridinium and1-morpholinocarbonyl-3-(sulfonatoaminomethyl). Examples of the activevinyl compounds include 1,3,5-triacryloyl-hexahydro-s-triazine,bis(vinylsulfone)methane andN,N′-methylenebis-[β-vinylsulfonyl]propionamide]. Examples of the activevinyl compounds include 2,4-dichloro-6-hydroxy-s-triazine. Aldehydes arepreferred, and glutaraldehyde is particularly preferred. Two or morecross-linking agents may be used in combination.

The amount of the cross-linking agent is in the range of preferably 0.1to 20 wt. %, and more preferably 0.5 to 15 wt. % based on the amount ofthe polymer. The amount of non-reacted cross-linking agent remaining inthe orientation layer is preferably not more than 1.0 wt. %, and morepreferably not more than 0.5 wt. % based on the amount of theorientation layer.

For forming the orientation layer, a coating solution containing thepolymer is applied on the transparent support. As the solvent of thesolution, an organic solvent (e.g., methanol) or a mixed solvent ofwater and an organic solvent is preferred. As the coating method, knownmethods such as spin-coating, dip-coating, curtain-coating,extrusion-coating, bar-coating and E-type coating can be adopted. TheE-type coating method is particularly preferred.

The applied solution is dried at a temperature of preferably 20 to 110°C., more preferably 60 to 100° C., and most preferably 80 to 100° C. Thetime for drying the applied solution is preferably in the range of 1minute to 36 hours, more preferably in the range of 5 to 30 minutes.

The rubbing treatment can be conducted in the known manner. The surfaceof the layer is rubbed with paper, cloth (gauze, felt, nylon, polyester)or rubber along a certain direction, so as to give the aligningfunction. Generally, the layer is rubbed several times with cloth onwhich fibers having the same length and thickness are provided.

In the optically anisotropic layer, the liquid crystal molecules areprovided on the orientation layer by which the molecules are aligned.The polymer of orientation layer and the multi-functional monomers inthe optically anisotropic layer may be co-polymerized, if needed.Further, the polymer of orientation layer may be cross-linked with thecross-linking agent.

The orientation layer has a thickness preferably in the range of 0.1 to10 μm.

[Optically Anisotropic Layer]

The optically anisotropic layer is formed from liquid crystal molecules.As the liquid crystal molecules, discotic or rod-like liquid crystalmolecules are preferably used.

Preferred examples of the rod-like liquid crystal molecules includeazomethines, azoxy molecules, cyanobiphenyls, cyanophenyl esters,benzoic esters, phenyl cyclohexanecarbonate esters,cycnophenylcyclohexanes, cyano-substituted phenylpyrimidines,alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolans andalkenylcyclohexylbenzonitriles. Further, some metal complexes areincluded in the rod-like liquid crystal molecules.

Descriptions of the rod-like liquid crystal molecules are found in“Kagaku-Sosetsu, Ekisho no Kageku” (written in Japanese), vol.22(1994),Chapters 4, 7 and 11; and “Ekisho Devise Handbook” (written inJapanese), chapter 3.

The discotic liquid crystal molecules are also described in variousdocuments (C. Destrade et al, Mol. Crysr. Liq. Cryst., vol. 71, page 111(1981) ; Japan Chemical Society, Quarterly Chemical Review (written inJapanese), chapter 5 and chapter 10, section 2 (1994) ; B. Kohne et al.,Angew. Chem. Soc. Chem. Comm., page 1794 (1985) ; and J. Zhang et al.,J. Am. Chem. Soc., vol. 116, page 2655 (1994) ).

The liquid crystal molecules preferably have double bonds as thefunctional groups. If so, the liquid crystal molecules can beco-polymerized with the multi-functional monomers in the opticallyanisotropic layer. Further, strong covalent bonds are formed not onlyamong the multi-functional monomers but also among the liquid crystalmolecules and between the liquid crystal molecules and themulti-functional monomers. Consequently, the mechanical strength ofoptical compensatory sheet can be remarkably improved by introducing thecross-linkable functional groups into the liquid crystal molecules.

A polymerizable group should be bound to a discotic core of the discoticliquid crystal molecule to cause the polymerization reaction of thecompound. However, if the polymerizable group is directly bound to thediscotic core, it is difficult to keep the alignment at thepolymerization reaction. Therefore, a linking group is introducedbetween the discotic core and the polymerizable group. Accordingly, thediscotic liquid crystal molecule having a polymerizable group(polymerizable discotic liquid crystal molecule) preferably is acompound represented by the following formula (IV):D(-L-Q)_(n)   (IV)in which D is a discotic core; L is a divalent linking group; Q is apolymerizable group; and n is an integer of 4 to 12.

Examples of the discotic cores (D) are shown below. In the examples, LQ(or QL) means the combination of the divalent linking group (L) and thepolymerizable group (Q).

In the formula, the divalent linking group (L) preferably is selectedfrom the group consisting of an alkylene group, an alkenylene group, anarylene group, —CO—, —NH—, —O—, —S— and combinations thereof. Thedivalent linking group (L) more preferably is a divalent linking groupcomprising at least two divalent groups selected from the groupconsisting of an alkylene group, an alkenylene group, an arylene group,—CO—, —NH—, —O— and —S—. The divalent linking group (L) furtherpreferably is a divalent linking group comprising at least two divalentgroups selected from the group consisting of an alkylene group, analkenylene group, an arylene group, —CO— and —O—. The alkylene grouppreferably has 1 to 12 carbon atoms. The alkenylene group preferably has2 to 12 carbon atoms. The arylene group preferably has 6 to 10 carbonatoms.

Examples of the divalent linking groups (L) are shown below. In theexamples, the left side is attached to the discotic core (D), and theright side is attached to the polymerizable group (Q). The AL means analkylene group or an alkenylene group. The AR means an arylene group.The alkylene group, the alkenylene group and the arylene group may havesubstituent groups (e.g., alkyl group).

L1: -AL-CO—O-AL-

L2: -AL-CO—O-AL-O—

L3: -AL-CO—O-AL-O-AL-

L4: -AL-CO—O-AL-O—CO—

L5: —CO-AR—O-AL-

L6: —CO-AR—O-AL-O—

L7: —CO-AR—O-AL-O—CO—

L8: —CO—NH-AL-

L9: —NH-AL-O—

L10: —NH-AL-O—CO—

L11 : —O-AL-

L12: —O-AL-O—

L13: —O-AL-O—CO—

L14: —O-AL-O—CO—NH-AL-

L15: —O-AL-S-AL-

L16: —O—CO-AR—O-AL-CO—

L17: —O—CO-AR—O-AL-O—CO—

L18: —O—CO-AR—O-AL'O-AL-O—CO—

L19: —O—CO-AR—O-AL-O-AL-O-AL-O—CO—

L20: —S-AL-

L21: —S-AL-O—

L22: —S-AL-O—CO—

L23: —S-AL-S-AL-

L24: —S-AR-AL-

Examples of the polymerizable groups (Q) in the formula (IV) are thesame as those described in the polymer for orientation layer (Q1 to Q6).

In the formula (IV), n is an integer of 4 to 12, which is determinedaccording to the chemical structure of the discotic core (D). The 4 to12 combinations of L and Q can be different from each other. However,the combinations are preferably identical.

The optically anisotropic layer can be formed by coating an orientationlayer with a coating solution containing the liquid crystal moleculesand, if needed, a polymerization initiator and optional additives.

The optically anisotropic layer has a thickness preferably in the rangeof 0.5 to 100 μm, more preferably in the range of 0.5 to 30 μm.

After the optically anisotropic layer is formed, the multi-functionalmonomers are polymerized. If the polymer for orientation layer or theliquid crystal molecules have polymerizable groups, they are alsopolymerized with the multi-functional monomers.

The polymerization reaction can be classified into a thermal reactionwith a thermal polymerization initiator and a photo reaction with aphoto polymerization initiator. A photo polymerization reaction ispreferred.

Examples of the photo polymerization initiators include α-carbonylcompounds (described in U.S. Pat. Nos. 2,367,661, 2,367,670), acyloinethers (described in U.S. Pat. No. 2,448,828), α-hydrocarbon substitutedacyloin compounds (described in U.S. Pat. No. 2,722,512), polycyclicquinone compounds (described in U.S. Pat. Nos. 2,951,758, 3,046,127),combinations of triarylimidazoles and p-aminophenyl ketones (describedin U.S. Pat. No. 3,549,367), acridine or phenazine compounds (describedin Japanese Patent Provisional Publication No. 60(1985)-105667 and U.S.Pat. No. 4,239,850) and oxadiazole compounds (described in U.S. Pat. No.4,212,970).

The amount of the photo polymerization initiator is preferably in therange of 0.01 to 20 wt. %, and more preferably in the range of 0.5 to 5wt. % based on the solid content of the coating solution.

The light irradiation for the photo polymerization is preferablyconducted with an ultraviolet ray.

The exposure energy is preferably in the range of 20 to 5,000 mJ percm², and more preferably in the range of 100 to 800 mJ per cm². Thelight irradiation can be conducted while the layer is heated toaccelerate the photo polymerization reaction.

A protective layer may be provided on the optically anisotropic layer.

(Polarizing Plate]

The polarizing plate comprises two transparent protective films and apolarizing membrane provided between the films. As the transparentprotective film, a cellulose acetate film is generally used. Asdescribed above, the transparent support of the optical compensatorysheet can serve as one of the protective films. In that case, theoptical compensatory sheet and the polarizing plate are usually combinedto form an elliptically polarizing plate, in which the transparent axisof the polarizing plate is essentially parallel to the slow axis of thetransparent support of the compensatory sheet.

The transparent protective film has a moisture permeability preferablyin the range of 100 to 1,000 (g/m²)/24 hours, more preferably in therange of 300 to 700 (g/m²)/24 hours.

Examples of the polarizing membranes include an iodine polarizingmembrane, a polyene polarizing membrane and a dichromatic dye polarizingmembrane. The iodine polarizing membrane and the dye polarizing membraneare generally prepared from polyvinyl alcohol films.

[Liquid Crystal Display]

The optical compensatory sheet or the polarizing plate equipped with theoptical compensatory sheet is preferably applied for a liquid crystaldisplay (particularly, a display of transmission type).

A liquid crystal display of transmission type comprises two polarizingplates and a liquid crystal cell provided between them. The liquidcrystal cell comprises a pair of electrode substrates and liquid crystalmolecules placed between them.

In the case where the optical compensatory sheet of the invention isused in the display, one compensatory sheet is placed between the celland one of the polarizing plates. Otherwise, two compensatory sheets areplaced on both sides of the cell (i.e., each sheet is placed between thecell and each polarizing plate).

In the case where the polarizing plate of the invention is used in thedisplay, the plate equipped with the compensatory sheet (accordingto-the invention) is used in place of one or each of the twoconventional polarizing plates. When the polarizing plate equipped withthe compensatory sheet according to the invention is used, the plate isplaced so that the compensatory sheet (which serves as a protectivefilm) may be on the side of the liquid crystal cell.

Examples of preferred display modes of liquid crystal cell include TNmode, ECB mode, VA mode and OCB mode. The VA mode include MVA mode.

In a liquid crystal cell of TN mode, rod-like liquid crystal moleculesare essentially horizontally oriented in twisted alignment with a twistangle of 60 to 120° when voltage is not applied. The liquid crystal cellof TN mode is widely used in color TFT liquid crystal displays, andhence is described in many publications.

In a liquid crystal cell of VA mode, rod-like liquid crystal moleculesare essentially vertically aligned.

The liquid crystal cell of VA mode include some types:

(1) A liquid crystal cell of VA mode in a narrow sense (described inJapanese Patent Provisional Publication No. 2(1990)-176625), in whichrod-like liquid crystal molecules are essentially vertically alignedwhile voltage is not applied, and the molecules are essentiallyhorizontally aligned while voltage is applied;

(2) A liquid crystal cell of MVA mode (described in SID97, Digest oftech. Papers, 28(1997), 845), in which the VA mode is modified to bemulti-domain type so as to enlarge the viewing angle;

(3) A liquid crystal cell of n-ASM mode (described in Nippon EkishoToronkai [Liquid crystal forum of Japan), Digest of tech. Papers (1998),58-59), in which rod-like liquid crystal molecules are essentiallyvertically aligned while voltage is not applied, and the molecules areessentially oriented in twisted multi-domain alignment while voltage isapplied;

(4) A liquid crystal cell of SURVAIVAL mode (published in LCDinternational 98); and

(5) A liquid crystal cell of CPA mode (SID01).

The liquid crystal cell of OCB mode is a liquid crystal cell of bendalignment mode in which rod-like liquid crystal molecules in upper partand ones in lower part are essentially aligned in reverse(symmetrically). A liquid crystal display having the liquid crystal cellof bend alignment mode is disclosed in U.S. Pat. Nos. 4,583,825 and5,410,422. Since rod-like liquid crystal molecules in upper part andones in lower part are symmetrically aligned, the liquid crystal cell ofbend alignment mode has self-optical compensatory function. Therefore,this mode is referred to as OCB (optically compensatory bend) mode. Theliquid crystal display of bend alignment mode has an advantage ofresponding rapidly.

The liquid crystal cell of TN mode is widely used in color TFT liquidcrystal displays, and hence is described in many publications.

The liquid crystal cell of ECB mode has been studied for long time, andhence is also described in many publications.

EXAMPLE 1

(Preparation of Cellulose Acetate Solution)

The following components were poured into a mixing tank, and stirred andheated to dissolve each component. Thus, a cellulose acetate solutionwas prepared. Cellulose acetate solution Cellulose acetate (acetic acidcontent: 60.9%) 100 weight parts  Triphenyl phosphate (plasticizer) 7.8weight parts  Biphenyldiphenyl phosphate (plasticizer) 3.9 weight parts Methylene chloride (first solvent) 300 weight parts  Methanol (secondsolvent) 54 weight parts 1-Butanol (third solvent) 11 weight parts(Preparation of Retardation Increasing Agent Solution)

16 Weight parts of the following retardation increasing agent, 80 weightparts of methylene chloride and 20 weight parts of methanol were pouredinto another mixing tank, and stirred and heated to prepare aretardation increasing agent solution.(Retardation Increasing Agent)

(Preparation of Transparent Support)

25 Weight parts of the prepared retardation increasing agent solutionand 475 weight parts of the cellulose acetate solution were mixed andstirred to prepare a dope. The amount of the retardation increasingagent was 3.0 weight parts based on 100 weight parts of celluloseacetate.

The prepared dope was cast onto a cooled drum caster, so as to form acellulose acetate film of transparent support.

The retardation values Re and Rth of the prepared cellulose acetate filmwere measured at the wavelength of 633 nm by means of an ellipsometer(M-150, Japan Spectrum Co., Ltd.), and found 10 nm and 81 nm,respectively.

(Formation of Undercoating Layer)

On the above-prepared cellulose acetate film, the following coatingsolution was applied in the amount of 28 ml/m², and dried to form agelatin layer of 0.1 μm thickness. Coating solution for firstundercoating layer Gelatin 0.542 weight part Formaldehyde 0.135 weightpart Salicylic acid 0.160 weight part Acetone 39.1 weight parts Methanol15.8 weight parts Methylene chloride 40.6 weight parts Water 1.2 weightpart(Formation of Second Undercoating Layer)

On the first undercoating layer, the following coating solution wasapplied in the amount of 7 ml/m², and dried to form a secondundercoating layer. Coating solution for second undercoating layer Thefollowing anionic copolymer  0.079 weight part Monoethyl citrate  1.01weight part Acetone 20 weight parts Methanol 87.7 weight parts Water 4.05 weight parts (Anionic copolymer)

(Formation of Backing Layer)

On the reverse surface of the film, the following coating solution wasapplied in the amount of 25 ml/m², and dried to form a backing layer.Coating solution for backing layer Cellulose diacetate (acetic acidcontent: 55%) 0.656 weight part Silica matting agent (mean grain size: 1μm) 0.065 weight part Acetone 67.9 weight parts Methanol 10.4 weightparts(Formation of Orientation Layer)

A coating solution of the following composition was coated on theabove-formed second undercoating layer by means of a wire bar coater of#16. The coating amount was 28 ml/m². The coated layer was dried withair at 60° C. for 60 seconds, and further air dried at 90° C. for 150seconds. The dried layer was rubbed along the longitudinal direction ofthe cellulose acetate film (transparent support). Coating solution fororientation layer The following denatured polyvinyl alcohol  8 weightparts Non-denatured polyvinyl alcohol (PVA217, Kayaku  2 weight partsCo., Ltd.) Water 361 weight parts Methanol 119 weight parts Glutaricaldehyde (cross-linking agent)  0.5 weight part (Denatured polyvinylalcohol)

(Formation of Optically Anisotropic Layer)

To prepare a coating solution, 41.01 g of the following discotic liquidcrystal compound, 2.03 g of ethylene oxide denaturedtrimethlolpropanetriacrylate (V#360, Osaka Organic Chemicals Co., Ltd.),2.03 g of dipentaerythritolhexaacrylate (KYARD-DPHA, Nippon Kayaku Co.,Ltd.), 0.90 g of cellulose acetate butyrate (CAB-551-0.2, EastmanChemical), 0.23 g of cellulose acetate butyrate (CAB-551-1, EastmanChemical), 1.35 g of a photopolymerization initiator (Irgacure 907,Ciba-Geigy) and 0.45 g of a sensitizer (Kayacure DETX, Nippon KayakuCo., Ltd.) were dissolved in 102 g of methyl ethyl ketone. The coatingsolution was then applied on the orientation layer by means of a wirebar coater of #4. The thus-treated film was fixed on a metal frame, andmaintained in a thermostat at 130° C. for 2 minutes to align themolecules of the discotic compound. The film was then irradiated at 80°C. (the temperature of the film was 100° C.) for 0.4 second with anultraviolet ray emitted from a high pressure mercury lamp of 120 W/cm,so as to polymerize the discotic liquid crystal molecules, themulti-functional monomer (dipentaerythritolhexaacrylate) and denaturedpolyvinyl alcohol (polymer for orientation layer). The film was cooledto room temperature. Thus, an optically anisotropic layer was formed toprepare an optical compensatory sheet.

The Re retardation value was measured at 633 nm, and found 48 nm. Theaverage angle (inclined angle) between the discotic plane and thetransparent support (cellulose acetate film) was 42°.

(Preparation of Polarizing Plate)

Iodine was adsorbed onto a stretched polyvinyl alcohol film to prepare apolarizing membrane.

The above-prepared optical compensatory sheet was laminated with apolyvinyl alcoholic adhesive onto one surface of the polarizingmembrane, so that the backing layer of the transparent support in thesheet might be contact with the membrane. The slow axis of thetransparent support was placed parallel to the transmitting axis of thepolarizing membrane.

A commercially available cellulose triacetate film (Fujitac TD80UF, FujiPhoto Film Co., Ltd.) was saponified, and then laminated as atransparent protective film on the other surface (on the surface onwhich the optical compensatory sheet was not laminated) of thepolarizing membrane. The slow axis of the transparent protective filmwas placed perpendicularly to the transmitting axis of the polarizingmembrane.

Thus, a polarizing plate having the optical compensatory sheet wasprepared.

(Test for Reworking)

The prepared polarizing plate (having the optical compensatory sheet)was laminated on a glass plate with an adhesive, so that thecompensatory sheet side of the polarizing plate might be on the side ofthe glass plate.

The polarizing plate on the glass plate was aged for 6 hours at 50° C.,5 atm. After the aging was completed, the temperature and the relativehumidity were set at 25° C. and 60%, respectively, and then thepolarizing plate was peeled from the glass plate.

With respect to 100 of the polarizing plates, this procedure wasperformed. As a result, all the polarizing plates were clearly peeledoff without breaking and leaving any fragment on the glass plate.

(Preparation of Liquid Crystal Display)

A pair of polarizing plates were removed from a commercially availableliquid crystal display of TN mode (6E-A3, Sharp Corporation). In placeof the removed polarizing plates, the above-prepared polarizing platewas laminated on each side of the liquid crystal cell with an adhesive,so that the compensatory sheet side of each polarizing plate might be onthe side of the cell. The polarizing plate on the viewing side and thaton the backlight side were placed so that the fast axes of the viewingside plate and the backlight side plate might be arranged in 0 mode.Thus, the liquid crystal display was prepared.

The viewing angle of the prepared liquid crystal display was measured bymeans of a measuring apparatus (EZ-Contrast 160D, ELDIM) when each ofeight tones of black (L1) to white (L8) was displayed. The viewing anglewas defined as the angle range giving a contrast ratio of 10 or morewithout reversing black tones (between L1 and L2).

As a result, wide viewing angles were obtained. The upward, downward andleftward-rightward viewing angles were 70°, 45° and 160°, respectively.

EXAMPLE 2

(Preparation of Cellulose Acetate Solution)

Two cellulose acetate solutions (dopes for inner and outer layers) wereprepared from the following compositions. The dope for inner layer wasfiltrated at 50° C. through a filter having absolute filtrationprecision of 0.01 mm [#63, Toyo Roshi Co., Ltd.], and that for outerlayer was filtrated at 50° C. through a filter having absolutefiltration precision of 0.0025 mm [FH025, Pole]. Cellulose acetatesolutions Inner Outer Cellulose acetate (acetic acid content: 60.5%) 100100 Triphenyl phosphate 7.8 7.8 Biphenyldiphenyl phosphate 3.9 3.9 Theretardation increasing agent used in Example 1 4.5 4.5 Methylenechloride (first solvent) 450 481 Methanol (second solvent) 39 42 (unit:weight part)(Preparation of Transparent Support)

A three-layered casting die was used. The dopes for inner layer and forouter layer were simultaneously cast onto a metal support from thecenter nozzle and the outer nozzles, respectively. The amounts of thedopes were controlled so that the inner layer has the thickness of 45 μmand the outer layer has the thickness of 5 μm. The formed film waspeeled off, and monoaxially (laterally) stretched by 30% by means of atenter. The film was stepwise dried at 70° C. for 3 minutes, at 120° C.for 5 minutes, and 130° C. for 30 minutes. Thus, a cellulose acetatefilm for the transparent support was prepared. The amount of the solventremaining in the film was 0.5 wt. %.

The retardation values Re and Rth of the prepared cellulose acetate filmwere measured at the wavelength of 633 nm by means of an ellipsometer(M-150, Japan Spectrum Co., Ltd.), and found 38 nm and 175 nm,respectively.

(Saponification of Transparent Support)

The transparent support was immersed in 2.0 N aqueous potassiumhydroxide solution at 25° C. for 2 minutes, and then neutralized withsulfuric acid. After washed with pure water, the support was dried. Thesurface energy of the transparent support was measured by the contactangle method, and found 63 mN/m.

(Formation of Orientation Layer)

The coating solution for orientation layer used in Example 1 was coatedon the saponified transparent support by means of a wire bar coater of#16. The coating amount was 28 ml/m². The coated layer was dried withair at 60° C. for 60 seconds, and further air dried at 90° C. for 150seconds. The dried layer was rubbed at an angle of 45° to thelongitudinal direction of the cellulose acetate film (transparentsupport).

(Formation of Optically Anisotropic Layer)

To prepare a coating solution, 41.01 g of the discotic liquid crystalcompound used in Example 1, 1.22 g of ethylene oxide denaturedtrimethlolpropanetriacrylate (V#360, Osaka Organic Chemicals Co., Ltd.),2.84 g of multi-functional monomers (NK ester/A-TMMT, Sin-NakamuraKagaku Kogyo Co., Ltd.), 0.90 g of cellulose acetate butyrate(CAB-551-0.2, Eastman Chemical), 0.23 g of cellulose acetate butyrate(CAB-551-1, Eastman Chemical), 1.35 g of a photopolymerization initiator(Irgacure 907, Ciba-Geigy) and 0.45 g of a sensitizer (Kayacure DETX,Nippon Kayaku Co., Ltd.) were dissolved in 102 g of methyl ethyl ketone.The coating solution was then applied on the orientation layer by meansof a wire bar coater of #4. The thus-treated film was fixed on a metalframe, and maintained in a thermostat at 130° C. for 2 minutes to alignthe molecules of the discotic compound. The film was then irradiated at80° C. (the temperature of the film was about 100° C.) for 0.4 secondwith an ultraviolet ray emitted from a high pressure mercury lamp of 120W/cm, so as to polymerize the discotic liquid crystal molecules, themulti-functional monomer and denatured polyvinyl alcohol (polymer fororientation layer). The film was cooled to room temperature. Thus, anoptically anisotropic layer was formed to prepare an opticalcompensatory sheet.

The Re retardation value was measured at 633 nm, and found 45 nm. Theaverage angle (inclined angle) between the discotic plane and thetransparent support (cellulose acetate film) was 39°.

(Preparation of Polarizing Plate)

The procedure in Example 1 was repeated except that above-preparedoptical compensatory sheet was laminated so that the slow axis of thetransparent support might be at an angle of 45° to the transmitting axisof the polarizing membrane. Thus, a polarizing plate was prepared.

(Test for Reworking)

The prepared polarizing plate (having the optical compensatory sheet)was laminated on a glass plate with an adhesive, so that thecompensatory sheet side of the polarizing plate might be on the side ofthe glass plate.

The polarizing plate on the glass plate was aged for 6 hours at 50° C.,5 atm. After the aging was completed, the temperature and the relativehumidity were set at 25° C. and 60%, respectively, and then thepolarizing plate was peeled from the glass plate.

With respect to 100 of the polarizing plates, this procedure wasperformed. As a result, all the polarizing plates were clearly peeledoff without breaking and leaving any fragment on the glass plate.

(Preparation of Liquid Crystal Cell of Bend Alignment)

On a glass plate having an ITO electrode, an orientation layer ofpolyimide was provided and subjected to a rubbing treatment. Thisprocedure was repeated to prepare two substrates, and the substrateswere arranged face-to-face so that the rubbing directions might beparallel and that the cell gap might be 6 μm. Between them, a liquidcrystal having An of 0.1396 (ZLI1132, Merck & Co., Inc.) was introducedto prepare a liquid crystal cell of bend alignment.

(Preparation of Liquid Crystal Display)

Two polarizing plates prepared above were laminated on the liquidcrystal cell of bend alignment so that the cell might be between theplates. The plates were arranged so that the optically anisotropic layerin each plate might face to the cell substrate and that the rubbingdirections of the cell and the optically anisotropic layer might bereversely parallel.

Voltage of a square wave (55 Hz) was applied to the liquid crystal cell.An image was displayed according to normally white mode (white: 2V,black: 5V). A ratio of the transmittance (white/black) was measured as acontrast ratio. The upward, downward, and leftward-rightward contrastratios were measured by means of a meter (EZ-Contrast 160D, ELDIM), andthe viewing angle giving a contrast ratio of not smaller than 10(without tone inversion in black displaying) was measured at eightdisplaying states of L1 (full black) to L8 (full white).

As a result, wide viewing angles were obtained. The upward, downward andleftward-rightward viewing angles were 80°, 80° and 80°, respectively.

EXAMPLE 3

(Preparation of Cellulose Acetate Solution)

A cellulose acetate solution (dope) of the following components wasprepared. Cellulose acetate solution Cellulose acetate (acetic acidcontent: 59.5%) 100 weight parts Triphenyl phosphate 7.8 weight partsBiphenyldiphenyl phosphate 3.9 weight parts The retardation increasingagent used in Example 1 2.0 weight parts Methylene acetate 306 weightparts Cyclohexanone 122 weight parts Methanol 30.5 weight parts Ethanol30.5 weight parts Silica fine particles (mean grain size: 20 nm) 1.0weight part(Preparation of Transparent Support)

The prepared dope was cast onto a metal support, and dried at 70° C. for3 minutes and at 120° C. for 5 minutes. The formed film was peeled fromthe support, and then further dried at 130° C. for 50 minutes to form acellulose acetate film of transparent support. The amount of remainingsolvent was 0.8 wt. %.

The retardation values Re and Rth of the prepared cellulose acetate filmwere measured at the wavelength of 633 nm by means of an ellipsometer(M-150, Japan Spectrum Co., Ltd.), and found 10 nm and 50 nm,respectively.

(Saponification of Transparent Support)

The transparent support was coated with 2.0 N aqueous potassiumhydroxide solution at 70° C. for 30 seconds. After washed with purewater, the support was dried. The surface energy of the transparentsupport was measured by the contact angle method, and found 65 mN/m.

(Formation of Orientation Layer and Optically Anisotropic Layer)

The procedures of Example 3 were repeated except that the undercoatinglayer was not provided, to form an orientation layer and an opticallyanisotropic layer on the saponified surface of the transparent support.Thus, an optical compensatory sheet was produced.

EXAMPLE 4

(Saponification of Transparent Support)

The transparent support prepared in Example 1 was coated with 1.5 Npotassium hydroxide solution (solvent: water/isopropylalcohol/polyethylene glycol=14/86/15) in the amount of 5 ml/m² at 60° C.for 10 seconds. After remaining potassium hydroxide was removed bywashing, the support was dried. The surface energy of the transparentsupport was measured by the contact angle method, and found 63 mN/m.

(Formation of Orientation Layer and Optically Anisotropic Layer)

The procedures of Example 1 were repeated except that the undercoatinglayer was not provided, to form an orientation layer and an opticallyanisotropic layer on the saponified surface of the transparent support.Thus, an optical compensatory sheet was produced.

(Test for Reworking)

The procedure in Example 1 was repeated, and thus, a polarizing platewas prepared.

The prepared polarizing plate (having the optical compensatory sheet)was laminated on a glass plate with an adhesive, so that thecompensatory sheet side of the polarizing plate might be on the side ofthe glass plate.

The polarizing plate on the glass plate was aged for 6 hours at 50° C.,5 atm. After the aging was completed, the temperature and the relativehumidity were set at 25° C. and 60%, respectively, and then thepolarizing plate was peeled from the glass plate.

With respect to 100 of the polarizing plates, this procedure wasperformed. As a result, all the polarizing plates were clearly peeledoff without breaking and leaving any fragment on the glass plate.

1. An optical compensatory sheet comprising a transparent support and anoptically anisotropic layer, wherein the optically anisotropic layer isformed from liquid crystal molecules and monomers having four or moredouble bonds, said monomers being polymerized to form a cross-linkedpolymer in the optically anisotropic layer, wherein the liquid crystalmolecules are discotic liquid crystal molecules, and wherein each of thediscotic liquid crystal molecules has a double bond, said discoticliquid crystal molecules and the monomers being co-polymerized in theoptically anisotropic layer.
 2. The optical compensatory sheet asdefined in claim 1, wherein an orientation layer is provided between thetransparent support and the optically anisotropic layer.
 3. The opticalcompensatory sheet as defined in claim 2, wherein the orientation layercomprises a polymer having double bonds at side chains, said polymer inthe orientation layer and the monomers in the optically anisotropiclayer being co-polymerized along an interface between the orientationlayer and the optically anisotropic layer.
 4. A liquid crystal displaycomprising two polarizing plates, a liquid crystal cell provided betweenthe plates, and at least one optical compensatory sheet placed betweenthe cell and at least one of the plates, said optical compensatory sheetcomprising a transparent support and an optically anisotropic layer,wherein the optically anisotropic layer is formed from liquid crystalmolecules and monomers having four or more double bonds, said monomersbeing polymerized to form a polymer in the optically anisotropic layer,wherein the liquid crystal molecules are discotic liquid crystalmolecules, and wherein each of the discotic liquid crystal molecules hasa double bond, said discotic liquid crystal molecules and the monomersbeing co-polymerized in the optically anisotropic layer.
 5. The liquidcrystal display as defined in claim 14, wherein the transparent supportof the optical compensatory sheet functions as a transparent protectivefilm of the polarizing plate.
 6. A process for preparation of an opticalcompensatory sheet comprising the steps of: forming an opticallyanisotropic layer comprising discotic liquid crystal molecules having adouble bond and monomers having four or more double bonds, andcopolymerizing the discotic liquid crystal molecules and the monomers toform a cross-linked polymer in the optically anisotropic layer.